WO2003055839A1 - Procede de separation de dimeres de butadiene de pentenoates d'alkyle - Google Patents

Procede de separation de dimeres de butadiene de pentenoates d'alkyle Download PDF

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Publication number
WO2003055839A1
WO2003055839A1 PCT/NL2002/000852 NL0200852W WO03055839A1 WO 2003055839 A1 WO2003055839 A1 WO 2003055839A1 NL 0200852 W NL0200852 W NL 0200852W WO 03055839 A1 WO03055839 A1 WO 03055839A1
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WO
WIPO (PCT)
Prior art keywords
alcohol
pentenoate
alkyl
distillation
mixture
Prior art date
Application number
PCT/NL2002/000852
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English (en)
Other versions
WO2003055839A8 (fr
Inventor
Hubertus Adrianus Smits
Gerardus Wilhelmus Adrianus Hangx
Johan Thomas Tinge
Michael Sebastiaan Doelman
Original Assignee
Dsm Ip Assets B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Priority to US10/498,885 priority Critical patent/US7388121B2/en
Priority to AU2002358345A priority patent/AU2002358345A1/en
Priority to KR1020047009554A priority patent/KR100936853B1/ko
Priority to EP02792101A priority patent/EP1456167A1/fr
Publication of WO2003055839A1 publication Critical patent/WO2003055839A1/fr
Publication of WO2003055839A8 publication Critical patent/WO2003055839A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond

Definitions

  • the invention relates to a process to separate butadiene dimers from a mixture comprising butadiene dimers and alkyl-3-pentenoate and/or isomers thereof.
  • a mixture is for example obtained by carbonylation of butadiene in the presence of an alcohol, described in WO-A-9506027 and EP-B-728732.
  • Butadiene dimers may for example be present as impurities in the butadiene feed and/or may be formed during the catalysed carbonylation reaction of butadiene. With butadiene dimers is meant any condensation product of two butadiene molecules.
  • butadiene dimers are 1-vinylcyclohexene, 1 ,5-cyclooctadiene, 4- vinylcyclohexene and ,3,7-octatriene. Frequent occurring butadiene dimers are 4- vinylcyclohexene and 1 ,3,7-octatriene.
  • the prior art does not provide a method for the separation of butadiene dimers from a mixture comprising butadiene dimers and alkyl- 3-pentenoate and/or isomers thereof.
  • butadiene dimers can act as catalyst poison or inhibitor in subsequent catalysed reactions of alkyl-3-pentenoate and/or isomers thereof, wherein metal catalysts are being used.
  • An example of such a subsequent catalysed reaction is the hydroformylation of alkyl-3-pentenoate in the presence of a catalyst comprising e.g. rhodium and an organic phosphorous containing ligand to produce alkyl-5-formyl-valerate, an intermediate in the preparation of ⁇ -caprolactam.
  • Butadiene dimers can form a complex with the metal of the catalyst blocking the coordination sites of the catalyst.
  • the resulting metal butadiene complex prevents that the alkyl-3-pentenoate enters the desired reaction pathway of hydroformylation, as such a pathway would require the energetically favoured coordinated butadiene dimer to be first displaced prior to reacting with the alkyl-3- pentenoate, carbon monoxide and hydrogen, the desired reaction pathway.
  • the alkyl-3-pentenoate and/or isomers thereof is of high purity.
  • butadiene dimers from a mixture comprising butadiene dimers and alkyl-3-pentenoate and/or isomers thereof by distillation is unsuitable on industrial scale since the boiling points of butadiene dimers and alkyl-3-pentenoate and/or isomers thereof are close to each other.
  • the boiling point at atmospheric pressure of 1 ,3,7-octatriene is 125 °C
  • of methyl-4- pentenoate is 126 °C
  • of 4-vinylcyclohexene is 128 °C
  • of 1 ,5-cyclooctadiene is 132 °C
  • of methyl-3-pentenoate is 136 °C
  • of 1-vinylcyclohexene is 145 °C.
  • the object of the invention is to provide a method for the separation of butadiene dimers from a mixture comprising butadiene dimers and alkyl-3- pentenoate and/or isomers thereof. This object is achieved in that the butadiene dimers are separated from said mixture by distillation in the presence of an alcohol and in that the distillation is effected at a bottom temperature of between 80 and 200°C.
  • a substantial lower boiling point is meant a boiling point at atmospheric pressure of at least 35 °C below the boiling point of the alkyl-3-pentenoate at atmospheric pressure.
  • Distillation of the mixture comprising butadiene dimers and alkyl-3- pentenoate and/or isomers thereof is performed with a bottom temperature between 80 and 200°C.
  • the bottom temperature is between 90 and 170°C. More preferably, the bottom temperature is between 100 and 150°C.
  • Alcohols which are employable in the process of the present invention will be well known compounds which are in general readily commercial available. Any alcohol that at atmospheric pressure has a boiling point that is at least
  • the boiling point of the alcohol at atmospheric pressure is at least 30 °C lower than the boiling point of the alkyl-3- pentenoate at atmospheric pressure.
  • a larger difference between the boiling point of the alkyl-3-pentenoate and that of the alcohol results in a more efficient separation of the butadiene dimers.
  • the alcohol is a monohydroxy aliphatic alcohol. More preferably, the alcohol is a monohydroxy aliphatic C1-C4 alkyl alcohol. Examples are methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-butanol, i-butanol. Most preferably the alcohol is methanol.
  • the aliphatic group of the alcohol corresponds with the alkyl group of the alkyl pentenoate compound. With an alkyl pentenoate compound is meant an alkyl-3-pentenoate or an isomer thereof.
  • an alcohol corresponding with the alkyl group of the alkyl-pentenoate compound is especially advantageous since then transesterification of the alkyl pentenoate compound with the alcohol does not result in a different alkyl pentenoate compound; different with respect to the alkyl group.
  • methanol is preferred.
  • the amount of the alcohol present in the mixture according to the invention is preferably an effective amount to form a butadiene dimers/alcohol mixture having a boiling point substantial lower than the boiling point of alkyl-3-pentenoate.
  • the distillation is performed in the presence of an excess molar amount of alcohol relative to the molar amount of butadiene dimers.
  • the molar amount of alcohol to the molar amount of butadiene dimers is at least 10 to 1.
  • the process of the present invention is performed in a distillation column.
  • the column may be any distillation column.
  • the distillation of the process of the present invention preferably is as a vacuum distillation.
  • the vacuum distillation is performed at a pressure between 0.001 MPa and 0.1 MPa, more preferably at a pressure between 0.01 MPa and 0.1 MPa.
  • the pressure refers to the pressure at the top of the distillation column.
  • a lower pressure is preferred since at a lower pressure a lower amount of alcohol can be used without deteriorating the separation of butadiene dimers from a mixture comprising butadiene dimers and alkyl-3-pentenoate and/or isomers thereof. From an economical point of view a higher pressure is preferred, since at a lower pressure a more expensive distillation equipment is required.
  • the mixture comprising butadiene dimers and alkyl-3-pentenoate and/or isomers thereof may be fed to the distillation column anywhere.
  • the alcohol may be present in the mixture that is fed to the distillation column and/or may be fed to the distillation column in a separate stream.
  • a separate alcohol stream is fed below or at the same height of the feeding point of the mixture to be treated with the process of the present invention, in order to obtain an optimal interaction between the mixture and the alcohol.
  • Mixtures comprising butadiene dimers and alkyl pentenoate may for example be obtained by carbonylation of butadiene in the presence of an alcohol. Exemplifying carbonylation processes are e.g. described in WO-A-9506027 and EP-B- 728732.
  • Suitable mixtures that can be treated with the process of the present invention are carbonylation reactor effluents or mixtures obtained after having separated the catalyst system.
  • the mixture of the present invention may comprise compounds such as a catalyst system and/or heavies. Heavies are compounds having a boiling point higher than the boiling point of M3P.
  • the amount of butadiene dimers present in the mixture according to the invention generally lies in the range of 0.0001 % - 10 % by weight. Usually the amount of butadiene dimers is between 0.001 % - 5 % by weight, and in particular between 0.01 % - 2 % by weight.
  • the alkyl-3-pentenoate can be represented by the following structural formula:
  • alkyl group in which the alkyl group is a C C alkyl group.
  • examples are methyl, ethyl, propyl, iso- propyl, n-butyl, iso-butyl or t-butyl.
  • the isomers of alkyl-3-pentenoate are alkyl-2- pentenoate and alkyl-4-pentenoate.
  • the amount of alkyl-3-pentenoates and/or isomers thereof present in the mixture according to the invention is not critical, general, it lies in the range of 10-90 % by weight.
  • the butadiene dimers/alcohol mixture obtained by the process of the present invention may be discarded or may be partly discarded and partly recycled for example into a carbonylation reactor in which butadiene is carbonylated in the presence of an alcohol to an alkyl pentenoate.
  • the butadiene dimers/alcohol mixture obtained with the process of the present invention is further subjected to a separation stage.
  • separation can advantageously be performed by distilling the butadiene dimers/alcohol mixture in the presence of dialkyl adipate resulting in a top fraction comprising most of the alcohol and a bottom section comprising most of the butadiene dimers and the dialkyl adipate.
  • the top fraction of this distillation may advantageously be recycled to a carbonylation reactor in which butadiene is carbonylated in the presence of an alcohol or it may be used to be fed to the distillation column in which butadiene dimers are separated from alkyl-3-pentenoate and/or isomers thereof.
  • the bottom fraction of the distillation column in which butadiene dimers are separated from the alcohol is preferably further treated in a distillation column resulting in a top fraction comprising most of the butadiene dimers and a bottom fraction comprising most of the dialkyl adipate. This bottom fraction is advantageously recycled to the distillation column in which butadiene dimers are separated from the alcohol.
  • Dialkyl adipate is a compound that for example can be formed through carbonylation of alkyl-4-pentenoate in the presence of an alcohol.
  • dimethyl adipate is formed as a by-product during carbonylation of butadiene in the presence of methanol aimed at the formation of methyl-3-pentenoate.
  • a mixture comprising butadiene dimers (BD), methyl-3-pentenoate and/or isomers thereof (MP), methanol (MeOH) and high boiling compounds (heavies) including dimethyl adipate (DMA) is fed to distillation column A through line 1.
  • the bottom fraction of distillation column A is fed to distillation column B through line 2.
  • MP is separated from the heavies.
  • the heavies are leaving distillation column B through line 3 and are partly purged and partly fed to distillation column C through line 4.
  • the top fraction of distillation column A comprising a BD/MeOH mixture, is fed to distillation column C through line 5.
  • MeOH is separated from BD in the presence of DMA.
  • the thus separated MeOH is preferably recycled to distillation column A, through line 6.
  • the bottom fraction of distillation column C, comprising BD and DMA, is fed to distillation column D through line 7.
  • D DMA is separated from BD.
  • the thus obtained DMA is preferably recycled to distillation column C through line 8.
  • Example I 202 g of a mixture comprising 3.3 % by weight of 4-vinylcycIohexene
  • VCH 0.4 % by weight of 1 ,3,7-octatriene (OCT), 41.6 % by weight of methyl-3- pentenoate (M3P) and isomers thereof (M2P and M4P) and 27 % by weight of methanol was distilled in a batch-wise operated distillation column having 35 equilibrium stages at a reflux ratio of 10 and at a pressure of 0.01 MPa.
  • the starting mixture also comprises 4.8 % by weight of butadiene, 8.6 % by weight of methoxy butenes, 7.2 % by weight of dimethyl adipate and 7.1 % by weight of other compounds.
  • Example I was repeated except that 102 g of a mixture comprising 4.4 % by weight of 4-vinylcyclohexene (VCH), 0.5 % by weight of 1 ,3,7-octatriene
  • OCT methyl-3-pentenoate
  • M3P methyl-3-pentenoate
  • M2P and M4P isomers thereof
  • 33 % by weight of methanol was distilled at a pressure of 0.05 MPa.
  • the starting mixture also comprises 6.3 % by weight of methoxybutenes and 1.1 % by weight of other compounds.
  • 4- vinylcyclohexene and 1 ,3,7-octatriene are distilled off and subsequently distillation fractions containing methyl-3-pentenoate and isomers thereof.
  • the results are given in Figure 3 for methanol (MeOH), butadiene dimers (BD), i.e. the sum of VCH and OCT, M3P and/or isomers thereof (MP), i.e. the sum of M3P, M2P and M4P.
  • BD butadiene dimers
  • MP isomers thereof
  • a mixture comprising 0.4 % by weight of 4-vinylcyclohexene (VCH), 0.1 % by weight of 1,3,7-octatriene (OCT), 37.7 % by weight of methyl-3-pentenoate (M3P) and isomers thereof (M2P and M4P) and 37 % by weight of methanol was fed to the top of a continuous operated distillation column in an amount of 2.5 kg/h.
  • the distillation column was a column packed with 5 meter Sulzer BX structured packing ® , having 30-35 equilibrium stages and a diameter of 5 cm. The distillation was performed without an external flux at a pressure of 0.045 MPa and a temperature of 120 °C at the bottom of the column and 45 °C at the top of the column.
  • Example III was repeated except that the distillation column was a column packed with 2.5 meter Sulzer BX structured packing ® , having 15-18 equilibrium stages.
  • the results are also given in Table I and show again that the butadiene dimers are distilled off together with the methanol (Table I, example IV, distillate data) and that the bottom stream containing methyl-3-pentenoate and isomers thereof contains less than 0.0002 wt% of butadiene dimers (Table I, example IV, bottom stream data).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de séparation de dimères de butadiène d'un mélange composé de dimères de butadiène et d'alkyl-3-pentenoate et/ou d'isomères de ceux-ci, lesquels dimères de butadiène sont séparés de ce mélange par distillation en présence d'un alcool, laquelle distillation est effectuée à une température au fond comprise entre 80 et 200 °C. Les dimères de butadiène fréquemment utilisés peuvent notamment être des 4-vinylcyclohéxène et 1,3,7-octatriène. On peut notamment utiliser comme alcool des alcools aliphatiques monohydroxy.
PCT/NL2002/000852 2001-12-21 2002-12-19 Procede de separation de dimeres de butadiene de pentenoates d'alkyle WO2003055839A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US10/498,885 US7388121B2 (en) 2001-12-21 2002-12-19 Process to separate butadiene dimers
AU2002358345A AU2002358345A1 (en) 2001-12-21 2002-12-19 Process to separate butadiene dimers from alkyl pentenoates
KR1020047009554A KR100936853B1 (ko) 2001-12-21 2002-12-19 알킬 펜테노에이트로부터 부타디엔 다이머의 분리 방법
EP02792101A EP1456167A1 (fr) 2001-12-21 2002-12-19 Procede de separation de dimeres de butadiene de pentenoates d'alkyle

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01205094 2001-12-21
EP01205094.4 2001-12-21

Publications (2)

Publication Number Publication Date
WO2003055839A1 true WO2003055839A1 (fr) 2003-07-10
WO2003055839A8 WO2003055839A8 (fr) 2003-11-13

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PCT/NL2002/000852 WO2003055839A1 (fr) 2001-12-21 2002-12-19 Procede de separation de dimeres de butadiene de pentenoates d'alkyle

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US (1) US7388121B2 (fr)
EP (1) EP1456167A1 (fr)
KR (1) KR100936853B1 (fr)
CN (1) CN1243710C (fr)
AU (1) AU2002358345A1 (fr)
MY (1) MY140400A (fr)
TW (1) TWI296616B (fr)
WO (1) WO2003055839A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259520A (en) * 1979-01-10 1981-03-31 Basf Aktiengesellschaft Preparation of butanedicarboxylic acid esters
WO1995006027A1 (fr) * 1993-08-23 1995-03-02 Dsm N.V. Procede de preparation d'un melange de pentenoates d'alkyle
US6010975A (en) * 1998-06-19 2000-01-04 Industrial Technology Research Institute Catalyst composition for preparing 3-pentenoic ester from butadiene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5495041A (en) * 1995-02-22 1996-02-27 Dsm N.W. Process for the preparation of a pentenoate ester

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259520A (en) * 1979-01-10 1981-03-31 Basf Aktiengesellschaft Preparation of butanedicarboxylic acid esters
WO1995006027A1 (fr) * 1993-08-23 1995-03-02 Dsm N.V. Procede de preparation d'un melange de pentenoates d'alkyle
US6010975A (en) * 1998-06-19 2000-01-04 Industrial Technology Research Institute Catalyst composition for preparing 3-pentenoic ester from butadiene

Also Published As

Publication number Publication date
TWI296616B (en) 2008-05-11
EP1456167A1 (fr) 2004-09-15
KR20040071224A (ko) 2004-08-11
MY140400A (en) 2009-12-31
KR100936853B1 (ko) 2010-01-14
CN1606542A (zh) 2005-04-13
WO2003055839A8 (fr) 2003-11-13
TW200410934A (en) 2004-07-01
CN1243710C (zh) 2006-03-01
US20050109605A1 (en) 2005-05-26
AU2002358345A1 (en) 2003-07-15
US7388121B2 (en) 2008-06-17

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